EP3026089B1 - Feuille adhésive auto-collante transparente - Google Patents

Feuille adhésive auto-collante transparente Download PDF

Info

Publication number
EP3026089B1
EP3026089B1 EP14829302.0A EP14829302A EP3026089B1 EP 3026089 B1 EP3026089 B1 EP 3026089B1 EP 14829302 A EP14829302 A EP 14829302A EP 3026089 B1 EP3026089 B1 EP 3026089B1
Authority
EP
European Patent Office
Prior art keywords
layer
adhesive sheet
transparent adhesive
recording layer
diffuse reflection
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
EP14829302.0A
Other languages
German (de)
English (en)
Other versions
EP3026089A1 (fr
EP3026089A4 (fr
Inventor
Shinichi Ono
Hidenao Takeuchi
Masahiko Yoshida
Hidenobu HARIMA
Takayuki Kimura
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Osaka Sealing Printing Co Ltd
Original Assignee
Osaka Sealing Printing Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Osaka Sealing Printing Co Ltd filed Critical Osaka Sealing Printing Co Ltd
Publication of EP3026089A1 publication Critical patent/EP3026089A1/fr
Publication of EP3026089A4 publication Critical patent/EP3026089A4/fr
Application granted granted Critical
Publication of EP3026089B1 publication Critical patent/EP3026089B1/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/06—Interconnection of layers permitting easy separation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/40—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
    • B41M5/42—Intermediate, backcoat, or covering layers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C09J7/24—Plastics; Metallised plastics based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/241—Polyolefin, e.g.rubber
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C09J7/24—Plastics; Metallised plastics based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/241—Polyolefin, e.g.rubber
    • C09J7/243—Ethylene or propylene polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C09J7/24—Plastics; Metallised plastics based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/245—Vinyl resins, e.g. polyvinyl chloride [PVC]
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/29—Laminated material
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/385—Acrylic polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/412—Transparent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/728—Hydrophilic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2405/00—Adhesive articles, e.g. adhesive tapes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M2205/00—Printing methods or features related to printing methods; Location or type of the layers
    • B41M2205/04—Direct thermal recording [DTR]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M2205/00—Printing methods or features related to printing methods; Location or type of the layers
    • B41M2205/36—Backcoats; Back layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M2205/00—Printing methods or features related to printing methods; Location or type of the layers
    • B41M2205/38—Intermediate layers; Layers between substrate and imaging layer
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2483/00—Presence of polysiloxane
    • C09J2483/005—Presence of polysiloxane in the release coating

Definitions

  • the present invention relates to a transparent adhesive sheet having excellent transparency and including an adhesive layer on the back surface side.
  • a transparent adhesive sheet is widely used as, for example, a transparent adhesive tape.
  • the transparent adhesive sheet is not only excellent in appearance, but also does not hide an adherend even after attached to the adherend. Therefore, its application is extraordinarily wide.
  • the transparent adhesive sheet often includes an adhesive layer formed with an adhesive agent on the back surface side.
  • a transparent adhesive sheet also includes, on the front surface side, a release layer containing a release agent having release properties to the adhesive agent.
  • the long transparent adhesive sheet configured as described above, which is wound around a core material, is commercially available. In such a wound state, the adhesive agent is in contact with the release layer of its immediately inner layer. This prevents the transparent adhesive sheet from being bonded to the transparent adhesive sheet itself. Therefore, a user can release the adhesive layer which has been temporarily bonded to the release layer, thereby using the transparent adhesive sheet sequentially from the outer circumferential side.
  • a release agent to be used in the release layer a water-repellent or oil-repellent component such as silicone resins and silicone oils is added. These release agents are likely to repel printed ink in general. Therefore, it is difficult to perform printing on the release layer. In order to prevent printing from being performed on the release layer, for example, it is also conceivable to previously perform printing on a layer to become a base material or the like and then forming the release layer or the adhesive layer. However, in this method, a request to perform printing when bonding the transparent adhesive sheet cannot be met.
  • thermosensitive recoding materials examples include JP H10 166730 A , US 2002/065197 A1 , EP 2 554 392 A1 , and JP 3 471 174B2 .
  • JP-A-2008-63520 laser beams are irradiated on a laminated deep-color ink layer to remove the irradiated portions.
  • a white or pale color ink layer laminated on the lower layer side of the deep-color ink layer in this manner, printing is performed. Therefore, the deep-color ink layer capable of absorbing laser beams needs to be formed. For this reason, a transparent adhesive sheet having a deep color as a whole can only be manufactured.
  • An object of the present invention is to provide a transparent adhesive sheet that can be used as a transparent adhesive tape and on which printing can be performed during in use.
  • the transparent adhesive sheet includes the recording layer containing a color developing material that thermally develops color. This enables thermal printing during in use. Also, the transparent adhesive sheet includes the base material layer formed with a transparent material and the recording layer that is transparent in a state before it develops color. Therefore, the transparent adhesive sheet can be used as a transparent adhesive tape. It is noted that as described herein, "transparent” includes “colorless transparent” and “colored transparent.”
  • Printing can be performed in a simple method when the transparent adhesive sheet according to the present invention is used. Therefore, the transparent adhesive sheet can be used as a transparent adhesive tape on which printing has been performed. Furthermore, since the transparent adhesive sheet has high transparency, an adherend is not hidden even when the transparent adhesive sheet is bonded to the adherend.
  • a front surface side and a back surface side refer to the directions indicated by arrows in the drawing.
  • FIG. 1 is a schematic cross-sectional view of a transparent adhesive sheet according to the present embodiment.
  • a transparent adhesive sheet 1 includes a base material layer 2 formed with a transparent material, an adhesive layer 6 formed on a back surface side of the base material layer 2 and formed with an adhesive agent for bonding to an adherend, a recording layer 3 formed on a front surface side of the base material layer 2 and containing a color developing material that thermally develops color, and a release layer 5 formed on the further front surface side of the recording layer 3 and having release properties to the adhesive agent.
  • This transparent adhesive sheet 1 further includes an intermediate layer 4 arranged on the front surface side of the recording layer 3 so as to be in contact with the recording layer 3.
  • the transparent adhesive sheet 1 is transparent as a whole in the state before the recording layer 3 develops color.
  • transparent means a state in which, when the transparent adhesive sheet 1 is bonded to an adherend such as a commercial product, the adherent can be visually recognized through the transparent adhesive sheet 1. Therefore, as described herein, “transparent” includes "colorless transparent” and "colored transparent.”
  • the opacity in accordance with JIS P8138 in the state before the recording layer 3 develops color is preferably not more than 25%. When the opacity falls within the above-described range, the transparent adhesive sheet has high transparency. The opacity is further preferably not more than 20%.
  • the opacity can be measured using, for example, a commercially available reflectometer. It is noted that JIS P8138 is a measurement standard for the opacity of paper. It is noted that when preprinting has been performed on a part of the transparent adhesive sheet 1, the opacity is measured in a part other than the preprinted part.
  • the transparent adhesive sheet 1 is long, and has a shape generally called a transparent adhesive tape.
  • This long transparent adhesive sheet 1 is wound around a core material 8 as illustrated in Fig. 2 to be supplied to a user.
  • a core material 8 inexpensive paper or the like is usually used.
  • resin or metal which can prevent deformation, can also be used depending on applications.
  • a cylindrical core material is often used.
  • any core material having a shape that allows the transparent adhesive sheet 1 to be wound around such as columnar, prismatic, and square tubular.
  • the length of the core material 8 may be the same as the length in the lateral direction of the transparent adhesive tape. However, the length of the core material 8 may be shorter or longer than the length in the lateral direction of the transparent adhesive tape, as long as it allows the transparent adhesive sheet 1 to be wound around.
  • the adhesive agent of the adhesive layer 6 is in contact with the release layer 5, except for a part which is brought into contact with the core material 8.
  • the release layer 5 has release properties to the adhesive agent. Therefore, the transparent adhesive tape is inhibited from adhering by the adhesive agent.
  • a user can sequentially peel off a necessary amount of the transparent adhesive tape from the exterior side of the wound tape toward the core material 8 side. Then, a user can cut away the peeled transparent adhesive tape, and use the cut adhesive tape.
  • the base material layer 2 is constituted by a transparent material, for example, a transparent resin film.
  • the resin constituting the base material layer 2 is not particularly limited as long as the film has flexibility and high transparency.
  • examples of such resin include polyolefin resins such as polyethylene and polypropylene, styrene resins such as polystyrene, polyester resins such as polyethylene terephthalate, and carbonate-based resins such as polycarbonate.
  • polyolefin resins such as polyethylene and polypropylene
  • styrene resins such as polystyrene
  • polyester resins such as polyethylene terephthalate
  • carbonate-based resins such as polycarbonate.
  • One of these resins may be used alone, or two or more thereof may be used in combination.
  • the resin film constituting the base material layer 2 may be an unstretched film or may be a stretched film.
  • the stretched film may be either a uniaxial stretched film or a biaxial stretched film.
  • the base material layer 2 may be either a single-layer film or a multi-layer film.
  • the thickness of the base material layer 2 is, for example, 5 to 150 ⁇ m, preferably 10 to 100 ⁇ m, and further preferably 20 to 70 ⁇ m.
  • the recording layer 3 is a layer for thermally develops color, and is disposed for enabling printing.
  • the disposition of the recording layer 3 allows, for example, a printer having a thermal head to be used so that the recording layer 3 develops color. This enables printing of letters or designs at an optional timing.
  • the recording layer 3 includes a color developing material that thermally develops color.
  • the color developing material is not particularly limited as long as it is a color developing material that can thermally develop color.
  • a color developing dye that can develop color alone may be used.
  • a combination of a transparent or pale color dye (leuco dye) and a developer that enables this dye to thermally develop color may be used.
  • a color developing material including the combination of a leuco dye and a developer, which is used in common thermal recording paper or the like, is readily available and has high versatility.
  • the leuco dye a known dye can be used.
  • the leuco dye include various leuco dyes based on triphenylmethane phthalide, triallyl methane, fluoran, phenothiazine, thiofluoran, xanthene, indophthalyl, spiropyran, azaphthalide, chromenopyrazole, methine, rhodamine anilinolactam, rhodamine lactam, quinazoline, diazaxanthene, and bislactone.
  • these leuco dyes one may be used alone. However, the use of a combination of two or more leuco dyes allows a recording layer which enables printing with a desired color to be formed.
  • a fluoran-based leuco dye and a phthalide-based leuco dye are preferred.
  • the fluoran-based leuco dye include 3-alkyl-2-anilino-6-(N,N-dialkylamino)fluoran such as 2-anilino-6-diethylamino-3-methylfluoran, 2-anilino-6-(N-n-propyl-N-methylamino)-3-methylfluoran, 2-anilino-6-(N-sec-butyl-N-ethylamino)-3-methylfluoran, 2-anilino-6-di(n-butyl)amino-3 -methylfluoran, and 6-(N-isopentyl-N-ethyl)amino-3-methyl-2-o-chloroanilinofluoran; 3-alkyl-2-anilino-6-(N-alkoxyalkyl-N-alkylamin
  • phthalide-based leuco dye examples include
  • 6-(dimethylamino)-3,3-bis[p-(dimethylamino)phenyl]phthalide (crystal violet lactone), 3-[2,2-bis(1-ethyl-2-methyl-3-indolyl)vinyl]-3-(4-diethylaminophenyl)phthalide, 3-[1,1-bis(4-diethylaminophenyl)ethylene-2-yl]-6-dimethylaminophthalide, 3,3-bis(1-n-butyl-2-methylindole-3-yl)phthalide, and 3,3-bis(4-diethylamino-2-ethoxyphenyl)-4-azaphthalide.
  • an electron acceptor such as an acidic substance may be used.
  • the developer may be appropriately selected depending on the type of the leuco dye.
  • a known developer may be used.
  • the developer include acidic inorganic matters (bentonite, zeolite, silica gel, and the like), and carboxylic acids (aliphatic mono-carboxylic acids such as stearic acid; polycarboxylic acids such as oxalic acid and maleic acid; aliphatic hydroxycarboxylic acids such as tartaric acid, citric acid, and succinic acid; and aromatic carboxylic acids such as benzoic acid), as well as compounds having a phenolic hydroxyl group.
  • One of these developers may be used alone, or two or more thereof may be used in combination.
  • Examples of the compounds having a phenolic hydroxyl group include hydroxyarene (for example, 4-tert-butylphenol, 4-phenylphenol, and ⁇ -naphthol); hydroxyarene carboxylic acids (for example, salicylic acid, 3-tert-butylsalicylic acid, 2-hydroxy-6-naphthoic acid, 2-hydroxy-p-tolilic acid, and 4-hydroxyphthalic acid); hydroxyarene carboxylic acid ester (for example, 5-hydroxyphthalic acid dimethyl, methyl-4-hydroxybenzoate, and 4-hydroxybenzoic acid ethyl); hydroxyarene carboxylic acid amide such as salicylanilide; metal salts of hydroxyarene carboxylic acids (for example, zinc salicylate, 2-hydroxy-6-zinc naphthoate, and 3,5-di-tert-tin butyl salicylate); bisphenols (for example, hydroxy biphenyl such as 2,2'-dihydroxydiphenyl,
  • the color developing material such as the leuco dye and the developer contained in the recording layer 3 are usually particulate. Therefore, even if the particles themselves of the color developing material are transparent, diffuse reflection of light causes the transparency of the transparent adhesive tape to be inhibited. Especially, when the particle diameter of the color developing material is large, the diffuse reflection of light is further increased by the particles. This causes the transparency of the transparent adhesive sheet 1 to be further reduced. To address this concern, the diffuse reflection can be suppressed by controlling to reduce the particle diameter of the color developing material. Accordingly, the transparency of the transparent adhesive sheet 1 can be increased.
  • the average particle diameter of the color developing material such as the leuco dye and the developer may be, for example, 0.1 to 1 ⁇ m, preferably 0.1 to 0.7 ⁇ m, and further preferably 0.1 to 0.6 ⁇ m. It is noted that as described herein, the average particle diameter refers to a 50% average particle diameter (median diameter) in a particle size distribution by volume standard measured using a Microtrac laser diffraction and scattering particle size analyzer.
  • the color developing temperature of the color developing material differs depending on the type of the color developing material.
  • the type of the color developing material may be appropriately selected such that heat is generated at a desired heat generation temperature corresponding to, for example, the temperature of a heating body such as a thermal head used in printing.
  • the content of the color developing material in the recording layer 3 can be appropriately selected according to, for example, the absorbance in the visible light range in a state where the color developing material develops color. This content is, for example, 10 to 70% by mass, preferably 20 to 60% by mass, and further preferably 30 to 50% by mass.
  • the recording layer 3 may include a binding agent for binding the color developing material.
  • a binding agent for binding the color developing material.
  • resins, macromolecules (synthetic macromolecules and natural macromolecules), and the like can be used.
  • Preferred examples of the binding agent include a hydrophilic or water-soluble binding agent, and a water-dispersible binding agent.
  • a binding agent examples include vinyl acetate resins or saponified products thereof (for example, homopolymers or copolymers of vinyl acetate, such as polyvinyl acetate, vinyl acetate-maleic anhydride copolymer, and vinyl acetate-vinyl chloride copolymer, polyvinyl alcohol (PVA), and modified PVA (saponified products of vinyl acetate copolymers)), olefin resins (for example, copolymers of olefin and a polymerizable unsaturated carboxylic acid or an anhydride thereof, such as isopropylene-maleic anhydride copolymer, isobutylene-maleic anhydride copolymer, diisobutylene-maleic anhydride copolymer, and methyl vinyl-maleic anhydride copolymer), styrene resins (for example, polystyrene, and copolymers of styrene and a polymeriz of
  • Examples of the polymerizable unsaturated carboxylic acid and an anhydride thereof as a copolymerizable monomer in the above-described binding agent include carboxylic acids having an ethylene-based unsaturated bond or an anhydride thereof, such as (meth)acrylic acid, maleic acid, fumaric acid, and maleic anhydride.
  • carboxylic acids having an ethylene-based unsaturated bond or an anhydride thereof such as (meth)acrylic acid, maleic acid, fumaric acid, and maleic anhydride.
  • a carboxyl group or an acid anhydride group is introduced in resin. This imparts hydrophilicity or water-solubility to resin.
  • acrylic acid and methacrylic acid are collectively referred to as (meth)acrylic acid.
  • acrylic acid ester and methacrylic acid ester are collectively referred to as (meth)acrylic acid ester. Furthermore, by introducing an amide group or an amino group into acrylamide resin, hydrophilicity and water-solubility can be imparted to the resin.
  • binding agents one may be used alone, or two or more may be used in combination.
  • acrylic resins, saponified products of vinyl acetate resins (for example, PVA and modified PVA), or rubber-like polymers such as SBR are preferably used.
  • the saponified products of vinyl acetate resins have high hydrophilicity or water-solubility. For this reason, the compatibility between the color developing material and the base material layer 2, and the film formation properties are high, thereby to be likely to increase transparency. Also, the use of acrylic resins or rubber-like polymers is likely to increase bonding properties while ensuring high transparency.
  • the amount of the binding agent relative to 100 parts by mass of the color developing material is, for example, 10 to 70 parts by mass, preferably 20 to 65 parts by mass, and further preferably 35 to 60 parts by mass.
  • the recording layer 3 may further include a filler and/or a lubricant.
  • the filler include inorganic fillers and organic fillers (for example, various resin particles including styrene resins such as polystyrene (PS), olefin resins such as polyethylene (PE), acrylic resins such as polymethyl methacrylate (PMMA), and urea resins).
  • the inorganic fillers include mineral-based fillers (for example, active terra alba, kaolin such as kaolinite, talc, clay, and diatomaceous earth), silicon-containing compounds (for example, silicon oxides such as white carbon and silica gel, and silicate salts such as aluminum silicate), and metal compounds (metal oxides such as magnesium oxide, aluminum oxide, titanium oxide, and zinc oxide, metal hydroxides such as magnesium hydroxide and aluminum hydroxide, and metal inorganic acid salts such as magnesium carbonate, calcium carbonate, and barium sulfate).
  • mineral-based fillers for example, active terra alba, kaolin such as kaolinite, talc, clay, and diatomaceous earth
  • silicon-containing compounds for example, silicon oxides such as white carbon and silica gel, and silicate salts such as aluminum silicate
  • metal compounds metal compounds (metal oxides such as magnesium oxide, aluminum oxide, titanium oxide, and zinc oxide, metal hydroxides such as magnesium hydroxide and aluminum hydroxide
  • the amount of the filler relative to 100 parts by mass of the color developing material is, for example, 5 to 40 parts by mass, and preferably 15 to 30 parts by mass.
  • the lubricant examples include waxes (for example, paraffin wax, ester waxes such as carnauba wax, and polyolefin waxes such as polyethylene wax), oil and fat (for example, higher fatty acids such as oleic acid, higher fatty acid salts (for example, metal soap such as zinc stearate), animal oil and fat such as whale oil, and vegetable oil and fat), and silicone oil.
  • waxes for example, paraffin wax, ester waxes such as carnauba wax, and polyolefin waxes such as polyethylene wax
  • oil and fat for example, higher fatty acids such as oleic acid, higher fatty acid salts (for example, metal soap such as zinc stearate), animal oil and fat such as whale oil, and vegetable oil and fat
  • silicone oil for example, one may be used alone, or two or more may be used in combination.
  • the amount of the lubricant relative to 100 parts by mass of the color developing material is, for example, 1 to 40 parts by mass, preferably 5 to 35 parts by mass, and further preferably 10 to 30 parts by mass.
  • the particle diameter of the particles is preferably small similarly to the color developing material, from the viewpoint of inhibition of diffuse reflection.
  • the average particle diameter of these particles is, for example, 1 ⁇ m or less, preferably 0.5 ⁇ m or less, and further preferably 0.4 ⁇ m or less.
  • the average particle diameter is preferably small.
  • the lower limit of the average particle diameter is, for example, 0.01 ⁇ m or more.
  • This recording layer 3 preferably contains a first diffuse reflection suppression component for suppressing the diffuse reflection in the transparent adhesive sheet 1. Such suppression of the diffuse reflection on the particles contained in the recording layer 3 further increases the transparency of the transparent adhesive sheet 1.
  • this first diffuse reflection suppression component preferably includes an organic material having a melting point lower than the color developing temperature of the color developing material.
  • the first diffuse reflection suppression component melts when the temperature reaches a temperature not lower than the melting point of the first diffuse reflection suppression component due to heating in, for example, a step of forming the recording layer 3, a step of forming the intermediate layer 4, the release layer 5, and the like, or a step of causing the color developing material to develop color.
  • the melted first diffuse reflection suppression component is embedded in a space between the particles contained in the recording layer 3 and in a space formed at an interface between the base material layer 2 and the recording layer 3, thereby reducing unevenness between the particles and at the interface. As a result, the diffuse reflection in the recording layer 3 and at the interface between the base material layer 2 and the recording layer 3 is suppressed. This can improve the transparency of the transparent adhesive sheet 1.
  • the melting point of the first diffuse reflection suppression component is preferably lower than the temperature when forming each layer, especially the recording layer 3, and the color developing temperature of the color developing material.
  • the melting point of the first diffuse reflection suppression component melts at least when printing is performed on the transparent adhesive sheet 1. Therefore, the above-described effect can be exerted.
  • An example of such a material includes an organic material.
  • this organic material include resins such as polyethylene, organic fillers, waxes, and/or oils and fats.
  • the first diffuse reflection suppression components one may be used alone, or two or more may be used in combination.
  • paraffins paraffin waxes
  • the melting point of the first diffuse reflection suppression component is further preferably lower than the temperatures when forming the recording layer 3, the intermediate layer 4, the release layer 5, and the like.
  • the first diffuse reflection suppression component melts when forming the layers, thereby enabling the above-described effect to be obtained.
  • the melting point of the first diffuse reflection suppression component is further preferably lower than the temperature when forming the recording layer 3.
  • the melting point of the first diffuse reflection suppression component which meets the above-described condition is specifically, for example, lower than 80°C, preferably 65°C or lower, and further preferably 50°C or lower.
  • the lower limit of the melting point of the first diffuse reflection suppression component is, but not particularly limited to, for example, 35°C or higher.
  • the form of the first diffuse reflection suppression component before melting in the recording layer 3 is preferably particulate.
  • the average particle diameter of the first diffuse reflection suppression component is, for example, 1 ⁇ m or less, preferably 0.05 to 0.5 ⁇ m, and further preferably 0.1 to 0.4 ⁇ m. When the average particle diameter falls within such a range, the first diffuse reflection suppression component is likely to be dispersed in the recording layer 3. Furthermore, when the first diffuse reflection suppression component melts, it can relatively uniformly melt. In addition, even when the first diffuse reflection suppression component exists in a particulate form in the recording layer 3 without melting, diffuse reflection is also likely to be suppressed.
  • the amount of the first diffuse reflection suppression component relative to 100 parts by mass of the color developing material is, for example, 1 to 40 parts by mass, preferably 5 to 35 parts by mass, and further preferably 10 to 30 parts by mass.
  • amount of the first diffuse reflection suppression component falls within such a range, diffuse reflection in the transparent adhesive sheet 1, particularly in the recording layer 3 or at the interface between the recording layer 3 and the base material layer 2, can be effectively suppressed without damaging the clarity of the print.
  • Such a first diffuse reflection suppression component may be a component independent from other components contained in the recording layer 3.
  • a component having another function may function as the first diffuse reflection suppression component.
  • a material which melts at relatively low temperature melts in, for example, the step of forming the recording layer 3, the step of forming the intermediate layer 4, the release layer 5, and the like, or the step of causing the color developing material to develop color. Therefore, such a material functions as the first diffuse reflection suppression component.
  • the above-described resins such as polyethylene, organic fillers, waxes, and oils and fats may function as the binding agent and/or as the first diffuse reflection suppression component.
  • constituent components are firstly dispersed in a dispersion medium to prepare a coating liquid.
  • the coating liquid is applied on a surface on the front surface side of the base material layer 2.
  • the coated film is dried.
  • a known mixer or a known pulverizer such as a sand mill and a bead mill may be used.
  • organic solvents such as alcohol, ketone, and nitrile may be used.
  • water is preferably used.
  • the coated film can be dried under atmospheric pressure or reduced pressure.
  • the temperature of the transparent adhesive sheet 1 during drying is higher than the melting point of the first diffuse reflection suppression component due to temperature control, the first diffuse reflection suppression component can be melted. Therefore, diffuse reflection can be effectively suppressed.
  • the temperature of the transparent adhesive sheet 1 needs to be controlled not to become excessively high. From such a viewpoint, the temperature may be appropriately selected within the range of, for example, 25 to 100°C. More specifically, the temperature is preferably 50 to 100°C, and further preferably 80 to 100°C.
  • the weight of the recording layer 3 per unit area of the base material layer 2 is, for example, 1 to 10 g/m 2 , and preferably 2 to 6 g/m 2 , in terms of dry weight.
  • the thickness of the recording layer 3 can be defined in an appropriate range. Therefore, printing properties and transparency are likely to be balanced.
  • an intermediate layer 4 is further disposed on the front surface side of the recording layer 3 so as to be in contact with the recording layer 3.
  • the intermediate layer 4 is not an essential structure.
  • the disposition of the intermediate layer 4 can protect the recording layer 3, thereby increasing the water resistance, oil resistance, chemical resistance, and the like, of the transparent adhesive sheet 1.
  • resin is preferably used.
  • the inclusion of resin may improve film formation properties of the intermediate layer 4.
  • resins which have been described as examples of the binding agent in the recording layer 3, and the like, can be used.
  • the transparent adhesive sheet 1 is likely to have increased water resistance.
  • hydrophilic resins, water-soluble resins, water-dispersible resins, or the like facilitates the improvement of oil resistance.
  • the intermediate layer 4 also preferably includes a second diffuse reflection suppression component for suppressing diffuse reflection in the transparent adhesive sheet 1.
  • a second diffuse reflection suppression component may be a component independent from other components contained in the intermediate layer 4.
  • a component having another function may function as the second diffuse reflection suppression component.
  • the above-described hydrophilic resins or water-soluble resins have high film formation properties. Therefore, such resins are likely to be impregnated into the recording layer 3, which is hydrophilic, when forming the intermediate layer 4 on the recording layer 3. This facilitates formation of the smooth intermediate layer 4.
  • Such formation of the smooth intermediate layer 4 suppresses diffuse reflection in the recording layer 3 and at an interface between the recording layer 3 and the intermediate layer 4. This can further enhance the transparency of the transparent adhesive sheet 1.
  • hydrophilic resins and water-soluble resins function as the second diffuse reflection suppression component for suppressing diffuse reflection in the transparent adhesive sheet 1.
  • acrylic resins As such hydrophilic resins or water-soluble resins, acrylic resins (particularly, for example, acrylic resins in which hydrophilic groups such as a carboxyl group, acid anhydride group, amino group, and amide group are introduced) is preferably used other than saponified products of vinyl acetate resins such as PVA. Saponified products of vinyl acetate resins, especially PVA having a high saponification degree, and the like, contain many hydroxyl groups. Therefore, these resins have high hydrophilicity and water-solubility.
  • Such hydrophilic resins and water-soluble resins may be contained as a shell material of a core shell-type particle.
  • the core material in this case is not particularly limited, and may be appropriately selected from the hydrophilic resins or water-soluble resins described above as examples. However, these resins preferably contain hydrophobic resins such as crosslinked resins.
  • hydrophobic resins such as crosslinked resins.
  • the inclusion of hydrophobic resins in a core allows the core to remain in the intermediate layer 4 even after the hydrophilic resins or water-soluble resins contained in the shell are impregnated into the recording layer 3. This can improve water resistance.
  • compatibility with the release layer 5 is high, diffuse reflection at, for example, the interface between the intermediate layer 4 and the release layer 5 can be suppressed.
  • An example of the core shell-type particles includes known core shell-type particles containing acrylic-based resins such as acrylamide resins (trade name "Barrier Star” (manufactured by Mitsui Chemicals, Inc.)).
  • the intermediate layer 4 can be formed by drying a coated film obtained by coating a surface on the front surface side of the recording layer 3 with a coating liquid containing resin.
  • the form of the coating liquid is, for example, a dispersion liquid or an emulsion.
  • a dispersion medium to be used in the coating liquid include the dispersion media described as examples in the recording layer 3.
  • the coating liquid may contain a surfactant and the like as necessary.
  • resin includes water-soluble resins or hydrophilic resins
  • the water-soluble resins or hydrophilic resins can be impregnated into the recording layer 3 during the drying of the coated film.
  • the drying condition is not particularly limited, as long as the dispersion medium in the coating liquid can be removed under the condition.
  • the drying condition may be the same as the drying condition when forming the recording layer 3.
  • the weight of the intermediate layer 4 per unit area of the recording layer 3 is, for example, 0.1 to 5 g/m 2 , and preferably 0.5 to 3 g/m 2 , in terms of dry weight. When the weight of the intermediate layer 4 falls within such a range, barrier properties are likely to be ensured while ensuring transparency.
  • An adhesive layer 6 contains an adhesive agent.
  • An example of a usable adhesive agent includes a known acrylic-based adhesive agent, silicone-based adhesive agent, and rubber-based adhesive agent.
  • the adhesive agent may be any of a solvent-type adhesive agent, a solventless-type adhesive agent, and an emulsion-type adhesive agent.
  • the adhesive layer 6 can be formed by coating a surface on the back surface side of the base material layer 2 with an adhesive agent.
  • the order of forming the adhesive layer 6 is not particularly limited.
  • the adhesive layer 6 may be formed before forming the recording layer 3.
  • the adhesive layer 6 can be formed after having formed the recording layer 3, the intermediate layer 4, or the release layer 5.
  • the weight of the adhesive layer 6 per unit area of the base material layer 2 is, for example, 1 to 20 g/m 2 , and preferably 5 to 15 g/m 2 , in terms of dry weight. When the weight of the adhesive layer 6 falls within such a range, appropriate adhesiveness and transparency are likely to be ensured.
  • a release layer 5 is formed on the front surface side of the recording layer 3.
  • the release layer 5 is disposed on the outermost front surface side to be released from the adhesive layer 6 when the wound transparent adhesive sheet 1 is used.
  • the release layer 5 contains a release agent or a mold release agent.
  • the release agent or the mold release agent include common silicone resins and fluorine resins, known as a release agent or a mold release agent for plastic molding.
  • these release agents one may be used alone, or two or more may be used in combination, depending on the type of the adhesive agent.
  • the release layer 5 may contain known additives, for example, a lubricant for enhancing the slip of a thermal head, as necessary.
  • a region where the release layer 5 is formed is not particularly limited, as long as the adhesive layer 6 can be easily released when the transparent adhesive sheet 1 is wound around.
  • the release layer 5 may be formed at least in a region on an exterior circumference facing to the adhesive layer 6.
  • the release layer 5 may be formed on a part of the outermost front surface side, or may be formed on the whole.
  • the release layer 5 can be formed by coating the outermost front surface side with a release agent and drying the coated film.
  • the weight of the release layer 5 is, for example, 0.1 to 5 g/m 2 , and preferably 0.1 to 2.5 g/m 2 , in terms of dry weight. When the weight of the release layer 5 falls within such a range, release properties and transparency are likely to be ensured.
  • Fig. 3 is a schematic view for explaining a method of printing on the wound transparent adhesive sheet 1 of Fig. 2 . It is noted that the wound transparent adhesive sheet 1 is sometimes referred to as merely a wound body 1a below.
  • the wound body 1a is the strap-shaped transparent adhesive sheet 1 wound around the core material 8.
  • the wound body 1a is attached to a thermal transfer printer, part of which is illustrated, in a state of being housed in a cassette 9.
  • the thermal transfer printer includes a drive roller 10b for unwinding the transparent adhesive sheet 1 from the wound body 1a, and a thermal head 10a for heating the transparent adhesive sheet 1.
  • the strap-shaped transparent adhesive sheet 1, which has been unwound from the wound body 1a by the drive roller 10b, is supplied to the thermal head 10a portion. In this manner, the transparent adhesive sheet 1 is heated by being brought into contact with the thermal head 10a.
  • the color developing material in the recording layer 3 of the transparent adhesive sheet 1 is heated by the thermal head 10a to develop color.
  • the transparent adhesive sheet 1 is discharged outside the thermal transfer printer. In this manner, the thermal transfer printer can simply perform printing on the transparent adhesive sheet 1 during in use. Therefore, the transparent adhesive sheet 1 is also likely to be used in a small amount of commercial products.
  • the second embodiment of the present invention will be described with reference to Fig. 4 . It is noted that the second embodiment is the same as the first embodiment except that the layer structure is partly different. Therefore, description on the same portion will be omitted. Also, the structure having the substantially same function will be described using the same reference numeral.
  • the transparent adhesive sheet 1 includes a protective layer 7, for protecting the recording layer 3 or the intermediate layer 4, on the front surface side of the intermediate layer 4.
  • the protective layer 7 is disposed for protecting the recording layer 3 and the intermediate layer 4. Also, the protective layer 7 sometimes has a function of increasing the contact properties between a heating body such as a thermal head and the transparent adhesive sheet 1 during printing so that the recording layer 3 smoothly develops color.
  • the protective layer 7 sometimes contains all or any of a filler, a binding agent, and a lubricant.
  • a filler can provide appropriate layer strength to the protective layer 7.
  • the filler can be appropriately selected from the examples described above on the recording layer 3.
  • organic fillers such as PS particles and PMMA particles, metal compounds (for example, metal salts) such as calcium carbonate, and the like are preferred.
  • the filler particularly preferably contains silicon oxide or colloidal silica that is a colloid of silicon oxide hydrate.
  • Colloidal silica generally has a small particle diameter. Therefore, diffuse reflection in the protective layer 7 is suppressed. As a result, the protective layer 7 has improved transparency. Accordingly, images and letters formed on the recording layer 3 located on the back surface side to the protective layer 7 are highly likely to be clearly recognized through the protective layer 7 from the front surface side.
  • the average particle diameter of colloidal silica is, for example, 500 nm or less, preferably 400 nm or less, and further preferably 300 nm or less.
  • the protective layer 7 may contain a group of particles of a plurality of colloidal silica each having a different particle size distribution.
  • a combination of colloidal silica having an average particle diameter of not less than 1 nm and less than 20 nm and colloidal silica having an average particle diameter of, for example, 20 to 500 nm, and preferably 20 to 100 nm may be used.
  • the use of such a combination of a group of small particles and a group of large particles facilitates maintenance of high transparency even while increasing the strength of the protective layer 7.
  • the content of the colloidal silica in the protective layer 7 is, for example, 10 to 65% by mass, preferably 10 to 60% by mass, further preferably 10 to 50% by mass, and particularly 25 to 50% by mass.
  • the strength of the protective layer 7 and the high transparency are likely to be balanced.
  • the binding agent in the protective layer 7 examples include acrylic resins such as poly(meth)acrylic acid, epoxy resins, and thermosetting resins such as phenolic resin, as well as the above-described examples of the binding agent in the recording layer 3.
  • thermosetting resins self-crosslinkable thermosetting resins may be used, or a composition containing a base resin and a crosslinking agent may be used.
  • An example of such a composition includes a composition containing an acrylic resin having a carboxyl group such as polyacrylic acid, and a crosslinking agent of a carboxyl group.
  • the crosslinking agent a known crosslinking agent such as ammonium zirconium carbonate can be used depending on the type of the functional group possessed by the base resin.
  • thermosetting resins a substance containing a curing agent, a curing accelerator, or the like may be used as necessary.
  • the binding agents one may be used alone, or two or more may be used in combination.
  • the content of the binding agent in the protective layer 7 is, for example, 10 to 70% by mass, preferably 20 to 60% by mass, and further preferably 25 to 50% by mass. Also, the amount of the binding agent relative to 100 parts by mass of colloidal silica in the protective layer 7 is, for example, 50 to 500 parts by mass, and preferably 80 to 200 parts by mass.
  • the lubricant can be appropriately selected from the examples described above on the recording layer 3.
  • the average particle diameter of the lubricant is, for example, 0.01 to 7 ⁇ m, and preferably 0.05 to 6 ⁇ m.
  • the amount of the filler other than colloidal silica and the lubricant, relative to 100 parts by mass of the colloidal silica is, for example, 1 to 40 parts by mass, preferably 5 to 35 parts by mass, and further preferably 10 to 30 parts by mass.
  • the amount of the filler and the lubricant falls within such a range, transparency is likely to be ensured while maintaining the strength of the protective layer 7.
  • constituent components of the protective layer 7 are firstly dispersed in a dispersion medium to prepare a coating liquid.
  • the coating liquid is applied on the surface on the front surface side of the recording layer 3 or the intermediate layer 4.
  • the coated film is dried.
  • the dispersion medium to be used in the coating liquid include the examples described above on the recording layer 3, and the like.
  • the drying condition is not particularly limited, as long as the dispersion medium in the coating liquid can be removed under the condition.
  • the drying condition may be the same as the drying condition when forming the recording layer 3.
  • the weight of the protective layer 7 per unit area is, for example, 0.1 to 5 g/m 2 , and preferably 0.5 to 2.5 g/m 2 , in terms of dry weight. When the weight of the protective layer 7 falls within such a range, transparency and appropriate strength are likely to be ensured.
  • the third embodiment of the present invention will be described with reference to Figs. 5 to 7 . It is noted that the third embodiment is the same as the second embodiment or the first embodiment except that the layer structure is partly different. Therefore, description of the same portion will be omitted. Also, a structure having the substantially same function will be described using the same reference numeral. It is noted that in the following description, a longitudinal direction and a transverse direction refer to the directions indicated by arrows in the drawing.
  • the adhesive layer 6 was formed on the whole surface of the outermost back surface side.
  • the adhesive layer 6 is formed on a part of the back surface side as illustrated in Fig. 5 .
  • the release layer 5 is formed on a part of the outermost front surface side corresponding to the portion of the outermost back surface side in which the adhesive layer 6 is formed. According to such a structure, the use amount of the adhesive agent for constituting the adhesive layer 6 and the use amount of the release agent for forming the release layer 5 may be reduced in some cases. Furthermore, the area of the adhesive layer 6 bonded to an adherend is small.
  • the transparent adhesive sheet according to the present embodiment can be suitably used for an application in which the transparent adhesive sheet 1 needs to be temporarily bonded to an adherend.
  • the transparent adhesive sheet 1 can be suitably used as a strapping sheet for a container as illustrated in Fig. 6.
  • Fig. 6 is a side view schematically illustrating the state when the transparent adhesive sheet 1 is bonded to a container.
  • the transparent adhesive sheet 1 is strapped around a container 20 including a lid body 20a and a container body 20b.
  • the adhesive layers 6 and 6 disposed on both ends are bonded to the bottom of the container body, so that the transparent adhesive sheet 1 straps and seals the container 20.
  • the transparent adhesive sheet 1 is transparent, and therefore never obscures the container 20. Therefore, the container 20 can be sealed, without damaging the design features of the container 20, in a state where the contents can be visually inspected. Furthermore, printing can be always performed on the transparent adhesive sheet 1. Therefore, the manufacture date or the like can be displayed when sealing.
  • the transparent adhesive sheet 1 according to such a form may be supplied in a shape of being wound around the core material 8 as illustrated in Fig. 2 .
  • the transparent adhesive sheet 1 according to such a form may also be supplied as a large-sized sheet as illustrated in Fig. 7 .
  • the adhesive layer 6 extends in the longitudinal direction on the back surface side at both ends and a center in the transverse direction of the transparent adhesive sheet 1.
  • This large-sized sheet is cut in the transverse direction (that is, cut along dashed line 27a) at a predetermined distance D along the longitudinal direction.
  • This large-sized sheet is also cut in the longitudinal direction (cut along dashed line 27b) so as to divide the adhesive layer 6 at the center in the transverse direction. Accordingly, the strap-shaped transparent adhesive sheet 1 can be obtained.
  • the release layer 5 is formed on the protective layer 7.
  • the release layer 5 may be formed so as to be in contact with the intermediate layer 4, while the protective layer 7 may be omitted in the portion where the release layer 5 is formed.
  • Such a structure can save the material and the like necessary for the formation of the protective layer 7.
  • the release layer 5 has a function equivalent to that of the protective layer 7, a problem does not particularly arise even if the protective layer 7 does not exist in the portion where the release layer 5 is formed.
  • the release layer 5 is formed in a part of the outermost front surface side corresponding to the portion of where the adhesive layer 6 is formed.
  • the release layer 5 may be formed on the whole of the outermost front surface side.
  • Such a structure can prevent a difference in gloss from being generated between the portion where the release layer 5 is formed and the portion where the release layer 5 is not formed.
  • the formation of the release layer 5 on the whole surface may facilitate manufacture in some cases.
  • layers other than the base material layer 2, the adhesive layer 6, the recording layer 3, and the release layer 5 are not essential. Such layers may be optionally combined depending on applications. For example, when sufficient transparency can be obtained while the protection of the recording layer 3 is sufficient for a certain application, the intermediate layer 4 may be omitted.
  • the transparent adhesive sheet 1 may include a layer other than the above-described layers.
  • the transparent adhesive sheet 1 may include, independently from the recording layer 3, a preprinting layer for previously printing images, letters, and the like.
  • the preprinting layer may be formed between any of the above-described layers as necessary.
  • the transparent adhesive sheet 1 is wound around the core material 8 to be supplied. Also, in the third embodiment, the transparent adhesive sheet 1 is supplied in a shape of a large-sized sheet. However, the transparent adhesive sheet 1 may be supplied in another shape. The transparent adhesive sheet 1 may be supplied in the most suitable shape corresponding to the application, transportation, convenience in handling, and the like.
  • each of the layers possessed by the transparent adhesive sheet 1 does not necessarily need to be disposed on the whole surface.
  • the recording layer 3 may be disposed only in and near the portion. Accordingly, the material and the like necessary for the formation of the recording layer 3 can be saved and reduced. Furthermore, the intermediate layer 4 and the protective layer 7 in the portion where the recording layer 3 is not formed may be omitted.
  • a coating liquid for the recording layer 3 was prepared by dispersing, in an appropriate amount of water, 12 parts by mass of 2-anilino-6-di(n-butyl)amino-3-methylfluoran (average particle diameter: 0.5 ⁇ m) as a leuco dye, 25 parts by mass of 3,3'-diallyl-4,4'-dihydroxydiphenylsulfone (average particle diameter: 0.4 ⁇ m) as a developer, 20 parts by mass of SBR (styrene butadiene rubber, Tg-3°C) as a binding agent, 10 parts by mass of kaolin (average particle diameter: 0.4 ⁇ m) as a filler, and 4 parts by mass of paraffin (melting point: 46°C, average particle diameter: 0.2 ⁇ m) as the first diffuse reflection suppression component.
  • SBR styrene butadiene rubber, Tg-3°C
  • kaolin average particle diameter: 0.4 ⁇ m
  • paraffin melting point: 46°C, average particle
  • the coating liquid A was applied on the whole surface on the front surface side of an OPP film (biaxial stretched polypropylene film, thickness 40 ⁇ m) as the base material layer.
  • the applied coating liquid A was dried to form the recording layer 3.
  • the coating liquid A was applied such that the applied amount of the coating liquid A becomes 4.0 g/m 2 in terms of the weight after drying.
  • a coating liquid for the intermediate layer 4 was prepared by dispersing, in an appropriate amount of water, a core shell-type acrylic resin as the first diffuse reflection suppression component.
  • the coating liquid B was applied on the whole surface on the front surface side of the recording layer 3 of the layered body obtained in the above-described (1).
  • the applied coating liquid B was dried to form the intermediate layer 4. At this time, the coating liquid B was applied such that the applied amount of the coating liquid B becomes 1.8 g/m 2 in terms of the weight after drying.
  • a coating liquid for the protective layer 7 was prepared by dispersing, in an appropriate amount of water, 15 parts by mass of colloidal silica having a particle diameter of several nm, 30 parts by mass of colloidal silica having a particle diameter of several tens nm, 10 parts by mass of PE particles (average particle diameter: 0.12 ⁇ m), 5 parts by mass of zinc stearate (average particle diameter: 5.5 ⁇ m), a binding agent (50 parts by mass of acrylic resin (polyacrylic acid), and 5 parts by mass of ammonium zirconium carbonate as a crosslinking agent).
  • the coating liquid C was applied on the whole surface on the front surface side of the intermediate layer 4 of the layered body obtained in the above-described (2).
  • the applied coating liquid C was dried to form the protective layer 7.
  • the coating liquid C was applied such that the applied amount of the coating liquid C becomes 1.5 g/m 2 in terms of the weight after drying.
  • the release layer 5 was formed by applying a silicone-based release agent (silicone resin) on the whole surface on the front surface side of the protective layer 7 of the layered body obtained in the above-described (3), such that the applied amount thereof becomes 0.5 g/m 2 .
  • a silicone-based release agent silicone resin
  • the adhesive layer 6 was formed by applying an acrylic-based adhesive agent on the whole surface on the back surface side of the base material layer of the layered body obtained in the above-described (4), such that the applied amount thereof becomes 10 g/m 2 . In this manner, a transparent adhesive sheet having a shape of an adhesive tape was prepared.
  • the obtained transparent adhesive sheet was measured for opacity in accordance with JIS P8138 using a reflectometer (manufactured by Tokyo Denshoku. co., Ltd., TC-6DS/A type reflectometer). As a result, the opacity was 7.4%.
  • a sensory test on whether an object can be visually recognized through a transparent adhesive sheet was performed in the following procedure.
  • a transparent adhesive sheet was placed at a distance of 1.5 cm from cooked rice as an object.
  • the cooked rice was visually observed through the transparent adhesive sheet from the release layer 5 side, and it was evaluated whether grains of the cooked rice can be recognized or not.
  • the evaluation was performed with five test subjects. As a result, all of the five test subjects were able to recognize the grains of the cooked rice.
  • Transparent adhesive sheets each having the opacity indicated in Table 1 were prepared in the same method as Example 1, except that the thickness of the base material layer was adjusted, and the applied amount of each layer was adjusted.
  • the transparent adhesive sheets of Examples 1 to 4 obtained as described above were transparent in the state before the recording layer 3 develops color.
  • the transparent adhesive sheet of Comparative Example 1 was opaque in the state before the recording layer 3 develops color.
  • the transparent adhesive sheets of Examples 1 to 4 had high transparency. Therefore, four or five out of five test subjects were able to visually recognize an object through the transparent adhesive sheet in the sensory test of visibility.
  • the transparent adhesive sheet of Comparative Example 1 was also opaque by visual inspection. As a result, five out of five test subjects were not able to recognize an object through the transparent adhesive sheet.
  • a transparent adhesive sheet was prepared by forming the intermediate layer 4 in the same method as Example 1, except that acrylic resin (Example 5), PVA (Example 6), or SBR (Example 7) was used in place of the core shell-type acrylic resin in (2) Formation of intermediate layer 4.
  • the obtained transparent adhesive sheet was evaluated in the same method as Example 1.
  • the opacity of the transparent adhesive sheet was not more than 10%. These adhesive sheets were excellent in transparency. In these Examples, high visibility, which was the same as Example 1, was exhibited.
  • the transparent adhesive sheets obtained in Examples 1 and 5 to 7 were evaluated for water resistance and oil resistance in the following procedure.
  • a transparent adhesive sheet was immersed in tap water at 23°C for 24 hours. Thereafter, the transparent adhesive sheet was removed from water, and it was confirmed whether or not the surface layer had fallen off due to a blister or the like (peeling of the surface).
  • Printing was performed on the recording layer 3 of a transparent adhesive sheet by a thermal transfer printer. Two drops of food oil were dropped on the surface of the transparent adhesive sheet where printing was performed, and allowed to stand at 40°C for 15 hours. Thereafter, the state of the type was checked.
  • the core shell-type particle is preferably used in the intermediate layer 4.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Adhesive Tapes (AREA)
  • Heat Sensitive Colour Forming Recording (AREA)
  • Laminated Bodies (AREA)

Claims (6)

  1. Feuille adhésive transparente (1) comprenant:
    une couche de matériau de base (2) formée d'un matériau transparent;
    une couche adhésive (6) formée d'un côté de la surface arrière de la couche de matériau de base (2) et formée d'un agent adhésif destiné à se coller à une surface d'adhérence;
    une couche d'enregistrement (3) formée d'un côté de la surface avant de la couche de matériau de base (2) et comportant un matériau de développement de couleur qui développe thermiquement la couleur;
    une couche antiadhésive (5) formée de l'autre côté de la surface avant de la couche d'enregistrement (3) et présentant des propriétés antiadhésives vis-à-vis de l'agent adhésif, et
    une couche intermédiaire (4) qui est disposée du côté de la surface avant de la couche d'enregistrement (3) de manière à être en contact avec la couche d'enregistrement (3),
    dans laquelle
    la couche intermédiaire (4) comporte un deuxième composant de suppression de réflexion diffuse destiné à supprimer la réflexion diffuse dans la feuille adhésive transparente (1),
    le deuxième composant de suppression de réflexion diffuse contient des résines hydrophiles ou des résines hydrosolubles,
    le deuxième composant de suppression de réflexion diffuse est constitué de particules de type enveloppe de noyau contenant, chacune, les résines hydrophiles ou les résines hydrosolubles dans une enveloppe,
    un diamètre de particule moyen du matériau de développement de couleur est de 0,1 à 1 µm, où le diamètre de particule moyen se réfère à un diamètre de particule moyen de 50% ou à un diamètre moyen dans une distribution de grosseurs de particule par volume standard mesuré à l'aide d'un analyseur de grosseurs de particules de diffraction et de diffusion à laser Microtrac,
    la feuille adhésive transparente (1) est transparente dans un état avant que la couche d'enregistrement (3) ne développe une couleur, et
    la feuille adhésive transparente (1) présente une opacité selon JIS P8138 de pas plus de 25% dans un état avant que la couche d'enregistrement (3) ne développe une couleur.
  2. Feuille adhésive transparente (1) selon la revendication 1, dans laquelle
    la couche d'enregistrement (3) comporte un premier composant de suppression de réflexion diffuse destiné à supprimer la réflexion diffuse dans la feuille adhésive transparente (1).
  3. Feuille adhésive transparente (1) selon la revendication 2, dans laquelle
    le premier composant de suppression de réflexion diffuse comporte un matériau organique présentant un point de fusion inférieur à une température de développement de couleur du matériau de développement de couleur.
  4. Feuille adhésive transparente (1) selon la revendication 3, dans laquelle le matériau organique contient de la paraffine.
  5. Feuille adhésive transparente (1) selon l'une quelconque des revendications 1 à 4, comprenant par ailleurs
    une couche de protection (7) qui protège la couche d'enregistrement (3) du côté de la surface avant de la couche d'enregistrement (3),
    dans laquelle
    la couche de protection (7) comporte un agent liant et une charge.
  6. Feuille adhésive transparente (1) selon l'une quelconque des revendications 1 à 5, dans laquelle
    la feuille adhésive transparente est enroulée autour d'une surface circonférentielle d'un matériau de noyau tubulaire ou en forme de colonne (8).
EP14829302.0A 2013-07-26 2014-07-25 Feuille adhésive auto-collante transparente Active EP3026089B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2013155982 2013-07-26
PCT/JP2014/069678 WO2015012386A1 (fr) 2013-07-26 2014-07-25 Feuille adhésive auto-collante transparente

Publications (3)

Publication Number Publication Date
EP3026089A1 EP3026089A1 (fr) 2016-06-01
EP3026089A4 EP3026089A4 (fr) 2017-03-29
EP3026089B1 true EP3026089B1 (fr) 2021-04-21

Family

ID=52393418

Family Applications (1)

Application Number Title Priority Date Filing Date
EP14829302.0A Active EP3026089B1 (fr) 2013-07-26 2014-07-25 Feuille adhésive auto-collante transparente

Country Status (7)

Country Link
US (1) US9902131B2 (fr)
EP (1) EP3026089B1 (fr)
JP (1) JP6153272B6 (fr)
KR (1) KR101824820B1 (fr)
CN (1) CN105555893B (fr)
ES (1) ES2879676T3 (fr)
WO (1) WO2015012386A1 (fr)

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105555893B (zh) 2013-07-26 2019-02-22 大阪希琳阁印刷株式会社 透明粘合片
JPWO2015072411A1 (ja) 2013-11-15 2017-03-16 大阪シーリング印刷株式会社 感熱記録シート
WO2016009462A1 (fr) * 2014-07-14 2016-01-21 大阪シーリング印刷株式会社 Corps d'enregistrement thermosensible
JP2016209126A (ja) * 2015-04-30 2016-12-15 ユニ・チャーム株式会社 吸収性物品及び吸収性物品の製造方法
FI3403946T3 (fi) * 2016-01-14 2023-10-11 Osaka Sealing Label Print Pakkausarkki ja pakkaussäiliö ja pakkausmenetelmä näitä hyväksikäyttäen
WO2017122312A1 (fr) * 2016-01-14 2017-07-20 大阪シーリング印刷株式会社 Corps d'impression thermosensible
JP2017181910A (ja) * 2016-03-31 2017-10-05 大阪シーリング印刷株式会社 透明シート連続体
KR102226498B1 (ko) * 2016-05-30 2021-03-11 캐논 가부시끼가이샤 인쇄물, 화상 기록 방법, 및 화상 기록 장치
DE102017131276A1 (de) * 2017-12-22 2019-06-27 Mitsubishi Hitec Paper Europe Gmbh Recyclingfähiges Releasesubstrat
JP7069446B2 (ja) * 2020-12-08 2022-05-18 大阪シーリング印刷株式会社 感熱フィルム
CN114536946A (zh) * 2022-01-17 2022-05-27 东莞市松烁硅胶科技有限公司 一种几何形硅胶胶章制备方法

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0825807A (ja) * 1994-07-20 1996-01-30 New Oji Paper Co Ltd 感熱記録体の製造方法

Family Cites Families (29)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01154791A (ja) * 1987-12-11 1989-06-16 Fuji Photo Film Co Ltd 受像材料および画像形成方法
JPH01156062A (ja) * 1987-12-14 1989-06-19 Oji Yuka Gouseishi Kk 半透明のプロピレン系樹脂多層複合フイルム
JPH03156406A (ja) 1989-11-15 1991-07-04 Hitachi Cable Ltd 多心光ロータリジョイント
US5210066A (en) 1989-12-28 1993-05-11 Mitsui Toatsu Chemicals, Inc. Heat-sensitive recording material
JP3050634B2 (ja) 1991-04-24 2000-06-12 日本化薬株式会社 感熱記録体
JP2730439B2 (ja) 1993-02-03 1998-03-25 株式会社日本触媒 感熱記録材料用水性樹脂分散液および該分散液を用いた感熱記録材料
US5380693A (en) * 1993-04-02 1995-01-10 Ricoh Company, Ltd. Transparent thermosensitive recording medium
US5840657A (en) * 1994-02-18 1998-11-24 The Standard Register Company Imagable linerless pressure sensitive adhesive
JP3471174B2 (ja) * 1996-06-25 2003-11-25 大阪シーリング印刷株式会社 感熱記録シート
JPH10166730A (ja) * 1996-12-13 1998-06-23 Oji Paper Co Ltd 感熱記録用粘着ラベル
JP3767059B2 (ja) 1997-01-07 2006-04-19 王子製紙株式会社 粘着シート
US5888929A (en) 1996-12-18 1999-03-30 Oji Paper Co., Ltd. Sheet set for temperature control and method of using the same
JPH10251591A (ja) 1997-03-14 1998-09-22 Nippon Shokubai Co Ltd 感熱記録材料用水性樹脂分散液、該分散液の製造方法、および該分散液を用いた感熱記録材料
JPH1156062A (ja) 1997-08-25 1999-03-02 Tadakatsu Ogura 草刈装置及び草刈装置用草刈カバー
JP3716084B2 (ja) 1997-09-30 2005-11-16 三菱製紙株式会社 可逆性感熱記録材料
JPH11165464A (ja) 1997-12-04 1999-06-22 Oji Paper Co Ltd 感熱記録体
JP2000273403A (ja) * 1999-03-26 2000-10-03 Lintec Corp 感熱発色テープ
WO2001016095A1 (fr) 1999-08-31 2001-03-08 Mitsubishi Paper Mills Ltd. Compose recepteur d'electrons et materiau pour thermogravure
WO2001054917A1 (fr) * 2000-01-28 2001-08-02 Sipix Imaging, Inc. Matiere d'enregistrement sensible a la chaleur
JP2001353964A (ja) 2000-06-13 2001-12-25 Osaka Sealing Printing Co Ltd 感熱発色記録ラベル
JP2002362027A (ja) 2001-06-07 2002-12-18 Oji Paper Co Ltd 感熱記録ラベル
JP2005040989A (ja) 2003-07-23 2005-02-17 Fuji Photo Film Co Ltd 感熱記録材料
JP2008063520A (ja) 2006-09-11 2008-03-21 Mitsubishi Pencil Co Ltd 粘着テープ
JP2010023252A (ja) 2008-07-16 2010-02-04 Oji Paper Co Ltd 感熱記録体
WO2011027752A1 (fr) 2009-09-03 2011-03-10 日本製紙株式会社 Etiquette d'enregistrement thermosensible
WO2011122552A1 (fr) * 2010-03-30 2011-10-06 三菱製紙株式会社 Matériau d'enregistrement thermosensible et procédé de fabrication associé
CN105555893B (zh) 2013-07-26 2019-02-22 大阪希琳阁印刷株式会社 透明粘合片
JPWO2015072410A1 (ja) 2013-11-15 2017-03-16 大阪シーリング印刷株式会社 透明感熱包装シート、ならびにこれを用いた透明包装容器および包装方法
JPWO2015072411A1 (ja) 2013-11-15 2017-03-16 大阪シーリング印刷株式会社 感熱記録シート

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0825807A (ja) * 1994-07-20 1996-01-30 New Oji Paper Co Ltd 感熱記録体の製造方法

Also Published As

Publication number Publication date
KR20160020544A (ko) 2016-02-23
US20160159035A1 (en) 2016-06-09
KR101824820B1 (ko) 2018-03-14
ES2879676T3 (es) 2021-11-22
JPWO2015012386A1 (ja) 2017-03-02
WO2015012386A1 (fr) 2015-01-29
CN105555893A (zh) 2016-05-04
JP6153272B2 (ja) 2017-06-28
JP6153272B6 (ja) 2018-06-27
EP3026089A1 (fr) 2016-06-01
CN105555893B (zh) 2019-02-22
EP3026089A4 (fr) 2017-03-29
US9902131B2 (en) 2018-02-27

Similar Documents

Publication Publication Date Title
EP3026089B1 (fr) Feuille adhésive auto-collante transparente
US9878567B2 (en) Thermal recording sheet
JPWO2015012386A6 (ja) 透明粘着シート
WO2015072410A1 (fr) Feuille d'emballage thermosensible transparente, et récipient d'emballage transparent ainsi que procédé d'emballage dans lequel est utilisée ladite feuille
JPWO2015072410A6 (ja) 透明感熱包装シート、ならびにこれを用いた透明包装容器および包装方法
JP6975510B2 (ja) ヒートシール用フィルム
JP6714945B2 (ja) 包装シート、ならびにこれを用いた包装容器および包装方法
JP3471174B2 (ja) 感熱記録シート
EP3403946B1 (fr) Feuille d'emballage, et récipient d'emballage et procédé d'emballage l'utilisant
JP6036352B2 (ja) 感熱記録体
JP2013199054A (ja) 感熱記録体
JP6015219B2 (ja) 感熱記録媒体
JP4440437B2 (ja) 感熱発色記録材
JP3410353B2 (ja) 感熱発色記録ラベル
JP2001232956A (ja) 転写可能な記録媒体
JP2020093499A (ja) 感熱配送伝票
JP2000326630A (ja) ２色感熱記録紙およびその製造方法
JP2004252225A (ja) 貼替防止ラベルおよび貼替防止ラベル連続体
JP2013199074A (ja) 感熱記録体
JP2013193455A (ja) 感熱記録体
JP2013043295A (ja) 画像形成方法、熱転写シート、及び熱転写受像紙
JP2014148118A (ja) 感熱記録体

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20160202

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

DAX Request for extension of the european patent (deleted)
A4 Supplementary search report drawn up and despatched

Effective date: 20170223

RIC1 Information provided on ipc code assigned before grant

Ipc: B41M 5/42 20060101ALI20170218BHEP

Ipc: B32B 7/06 20060101ALI20170218BHEP

Ipc: B41M 5/28 20060101ALI20170218BHEP

Ipc: B32B 7/12 20060101ALI20170218BHEP

Ipc: B41M 5/30 20060101ALI20170218BHEP

Ipc: C09J 7/02 20060101AFI20170218BHEP

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: EXAMINATION IS IN PROGRESS

17Q First examination report despatched

Effective date: 20190507

REG Reference to a national code

Ref country code: DE

Ref legal event code: R079

Ref document number: 602014076860

Country of ref document: DE

Free format text: PREVIOUS MAIN CLASS: C09J0007020000

Ipc: C09J0007240000

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

RIC1 Information provided on ipc code assigned before grant

Ipc: B41M 5/28 20060101ALI20201016BHEP

Ipc: B32B 7/06 20190101ALI20201016BHEP

Ipc: B41M 5/42 20060101ALI20201016BHEP

Ipc: C09J 7/24 20180101AFI20201016BHEP

Ipc: B32B 7/12 20060101ALI20201016BHEP

Ipc: C09J 7/29 20180101ALI20201016BHEP

Ipc: C09J 7/38 20180101ALI20201016BHEP

Ipc: B41M 5/30 20060101ALI20201016BHEP

INTG Intention to grant announced

Effective date: 20201106

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602014076860

Country of ref document: DE

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 1384624

Country of ref document: AT

Kind code of ref document: T

Effective date: 20210515

REG Reference to a national code

Ref country code: FI

Ref legal event code: FGE

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG9D

Ref country code: SE

Ref legal event code: TRGR

REG Reference to a national code

Ref country code: NO

Ref legal event code: T2

Effective date: 20210421

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20210421

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210421

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210421

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210421

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210721

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2879676

Country of ref document: ES

Kind code of ref document: T3

Effective date: 20211122

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210821

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210421

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210722

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210421

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210823

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210421

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602014076860

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210421

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210421

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210421

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210421

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210421

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210421

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20220124

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210421

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210821

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20210725

Ref country code: AL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210421

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20210725

REG Reference to a national code

Ref country code: AT

Ref legal event code: UEP

Ref document number: 1384624

Country of ref document: AT

Kind code of ref document: T

Effective date: 20210421

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20140725

P01 Opt-out of the competence of the unified patent court (upc) registered

Effective date: 20230509

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210421

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NO

Payment date: 20230714

Year of fee payment: 10

Ref country code: IT

Payment date: 20230727

Year of fee payment: 10

Ref country code: ES

Payment date: 20230801

Year of fee payment: 10

Ref country code: CH

Payment date: 20230801

Year of fee payment: 10

Ref country code: AT

Payment date: 20230719

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 20230713

Year of fee payment: 10

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210421

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210421

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210421

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20240708

Year of fee payment: 11

Ref country code: FI

Payment date: 20240724

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20240723

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 20240724

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20240724

Year of fee payment: 11